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Toxicity of decomposition products: phenolic resin
-
.--
d o c
:r
TOXICITY OF DECOMPOSITION FRODU(;TS - PIIENOLIC R E 5 I N
by
Y. Tsuchiya and K. Sumi
T o x i c gases and vapours produced by f i r e s are r e s p o n s i b l e f o r t h e majority o f deaths i n b u i l d i n g fires. In t h i s Mote, experimental
data on the t o x i c decomposition (combustion a n d p y r o l y s i s ) products of
phenol-formaldehyde r e s i n (phenolic r e s i n ) a r e presented and t h e t o x i c
h a z a r d created by t h e products i s e v a l u a t e d . P h e n o l i c r e s i n s are used in t h e b u i l d i n g i n d u s t r y as foam insulation and adhesives for laminates.
Experimental
One of the phenolic foams a v a i l a b l e on t h e market w a s used
without f u r t h e r treatment i n t h e p r e s e n t s t u d y . I n preliminary work, some r e s i n s were prepared in t h e l a b o r a t o r y and examined. The r a t i o of various phenols in t h e decomposition p r o d u c t s v a r i e d depending on t h e
composition o f the r e s i n , b u t t h e variation was not s i g n i f i c a n t from the t o x i c i t y p o i n t of view.
Combustion and pyrolysis experiments were carried out using
flow of a i r and n i t r o g e n respectively. The a p p a r a t u s w a s the same as The one described in a previous paper (1). The condensable p r o d u c t s were t r a p p e d in a U-tube cooled a t d r y i c e temperature and nan-canden-
sable gases were collected i n a p l a s t i c bag. The products were t h e n q u a n t i t a t i v e l y analyzed by gas chromatography. The d e t a i l s o f t h e a n a l y s i s are g i v e n in t h e Appendix.
Result and Discussion
Formaldehyde, phenols and o x l d e s of carbon were expected to be the main t o x i c decomposition p r o d u c t s o f p h e n o l i c resin. The y i e l d of formaldehyde was n e g l i g i b l e . P h e n o l s c o n s t i t u t e d the major p r o d u c t s ;
they were phenol, o-cresol, p - c r e s o l , 2,4-xylenol, 2,G-xylenol and
2,4,6-trimethyl phenol, approximately
in
descending o r d e r o f quantity,The experimental data on t h e s p e c i e s and relative q u a n t i t i e s were in
good agreement w i t h t h e d a t a presented by S h a r i f i and Tirgan (2) who
used pyrolysis gas chromatography. The total quantity of phenols and
given i n Table 1. 'The maximum y icltl o f ~ ~ h c n o l s wiis foulid :~t 700°C i n
the present study. According t o thc :!hove l i t e r a t u r e , phenols decompose to less t o x i c aromatic hydrocarbons a t h i g h e r temperatures.
T o x i c i t y due to these p r o d u c t s expressed as t o x i c i t y index
( 3 ) * i s given in T a b l e 2. I n t h e calculation o f t o x i c i t y index,
=f'
t h e concentration of t o x i c gases f a t a l to man i n 30 minutes is needed. Fop carbon monoxide and carbon d i o x i d e the values were assumed to be4,000 ppm and 85,000 pprn respectively [4,5). Unfortunately, there i s very little information a v a i l a b l e f o r t h e acute t o x i c i t y sf phenols.
The very approximate relation between t h r e s h o l d limit values and acute
t o x i c concentrations s u g ~ e s t t h a t cf o f phenol and cresols l i e between
200 pprn and 2000 ppm. The value 200 ppm was taken f o r the phenols in
t h e calculations s o that the results will be in the d i r e c t i o n of over- estimating the t o x i c i t y . The combined t o x i c i t y index of phenols based on experimental data from combustion o f phenolic resin in air w a s o f the same o r d e r as the t o x i c i t y index o f CO. The t o x i c i t y index o f phenols w a s somewhat greater when the resin was pyrolyzed
i n
an i n e r t atmosphere.The maximum value of t h e t o x i c i t y i n d e x of p h e n o l i c resin o b t a i n e d in
t h i s s t u d y was 27!tg-l. This f i g u r e i s less than t h a t of white p i n e (50Jlg-') and PVC (360!Zg-l) reported e a r l i e r ( 1 ) .
Conclusions
1 . A study concerning the t o x i c decompositfan p r o d u c t s af p h e n o l i c
resin was u n d e r t a k e n . The major products were phenol, cresols, xylenols and oxides of c a r b o n .
2. The maximum t o x i c i t y index due t o decomposition products of phenolic
resin was about 3 0 ~ ~ ' . This f i g u r e is l e s s than that o f white pine ( 5 0 ~ ~ - I ) and PVC (360tg-') indicating t h a t the propensity of phenolic resin
for
g e n e r a t i n g toxic decomposition products is lessthan t h a t of t h e t w o o t h e r materials.
v
*
The relationship T =-
wa5 used, where cfh7T = t o x i c i t y index
v
= volume o f a t o x i c component producedcf = concentration in volume r a t i o of t h e same component that is fatal to man i n 30 m i n u t e s
Acknowledgement
The
authors
wish t o thank Mr. .I. Boulanger and Mr. D.lrl. Morwickfor assistance
in conducting t h e experiments.References
1. Sumi, K. a n d T s u c h i y a , Y . , Toxicity o f Decomposition Products PVC
and Wood, Building Research Note f99. DBRJNRC, Ottawa, May 1975.
2 . Sarifi, N. and Tixgan, M . R . , J o u r n a l of Appl. Polyrn. S c i . ,
17,
1113, (19733.
3 . Sumi, K. and T s u c h i y a , Y., T o x i c i t y of Decomposition Products, .
.
Combustion Toxicolo-gy
-
2, 213, (1975) (NRCC 1 4 8 8 5 ).
4 . Henderson,Y.
and Haggard, Il.W., Noxious Gases, p . 110,Chem. C a t a l o g Company, New York, 1 9 2 7 .
5. Documentation o f t h e T h r e s h o l d L i m i t Values, Amcr. Cmf. Govern.
TABLE 1
Decomposition Products of Phenolic Resin
.
AtmosphereNz
Flow Rate cm3 min-' SO0 Temperature "C 400 500 6 0 0 706 6 . I 3.0 5 . 4 3 . 3 0.8 0 . 2 800 800I
~ r o d u c t s sample 800 A i r 9.6 2 . 9 4.5 6 . 2 3 2 . 9 500 200 500 1000 2000 4000 Phcnols 4 75 473 4 38 38 3 31 4 24 8 400 500 600 700 8 1 28 56 40 46 18 CO C 0 2 246 6 3 164 309 712 969 0.3 9 . 4 18.0 21.0 Residue 5 10 700 615 5 20 485 4 4 8 850 7 15 5 75 5 35 1 5 1 0 2 5 2 0 1 2 3 1 45 1 5 7 9 24 105 217 274TABLE 2
U C O N 5 0 - H B - 2 0 0 0 C O L U M N A T 1 6 0 c " C
R E T E N T I O N I N D E X
F I G U R E 1
G A S
C H R O M A T O G R A P H
A N A L Y S I S O F
P H E N O L S
P R O D U C E D
FROM P H E N O L I C R E S I N A T 7 0 0 " ~
I N
A I R
ANALYSIS OF THE
DECOMPOSITION
PRODUCTSOF
PI-IENOLIC RESINGas chromatography was the p r i n c i p a l technique f o r the analysis. The experimental c o n d i t i o n s a r e given i n T a b l e A - l .
Pheno 1 s
Phenols were s e p a r a t e d u s i n g gas chromatagraphic condition No. 1, Identification of each peak was carried out by injecting pure chemicals. R e t e n t i o n i n d i c e s and r e l a t i v e amounts of phenols generated
at 700'C w i t h 500 cm3Jmin f l o w sf air are shown in F i g u r e I . For the
quantitative analysis, over-all sensitivity of the GC detection was
determined by i n j e c t i n g known q u a n t i t y of o - c r e s o l . The same
quantitative response was assumed f o r a l l the o t h e r p h e n o l s because the theoretical values of s u b s t a n c e s p e c i f i c c o r r e c t i o n f a c t o r for flame
ionization detector were in agreement within a 2 p e r c e n t range.
Formaldehyde
Exhaust gas flow from combustion t u b e was introduced d i r e c t l y
into 1 ml. o f ice-coaled d i s t i l l e d warer. Formaldehyde if p r e s e n t in
t h e gas, dissolves i n t o the water. The water was then analyzed by GC
w i t h a Porapak N e a l v m and a thermal c o n d u c t i v i t y d e t e c t o r . Quantita- t i v e response was determi-ned by injecting a reagent grade formaldehyde
s o l u t i o n . Formaldehyde was e l u t e d f i r s t followed b y water and methanol ( s t a b i l i z e r for formaldehyde in t h e s o l u t i o n ) . Minimum detectable limit
SCOT, 100 ft- 0 . 0 2 i n . I D WS CMROMATOGIMPHIC CONDITIONS S t a t i o n a r y Phase - - Tempera- t u r e UCON O i l SO-!ID- 200.0 blolcculas s i cvc 5A Porapak N Porapak N
